Vat dyestuffs of the anthraquinone series



Patented Jan. 8, 1,946

VAT DYESTUFFS OF THE AN THRAQUINONE SERIES Werner Zerweck and Ernst Honold, Frankforton-the-Main-Fec'henheim, Germany, assignors to General Aniline & Film Corporation, New York, N Y., a corporation of Delaware No Drawing. Application May 17, 1940, Serial N- 335,760. In Germany June 6, 1939 4 Claims.

Our present invention relates to vat dyestuffs of the anthraquinone series more particularly to those of the general formula:

wherein R stands for a member of the group consisting of hydrogen and the, radicle of an amine of a vattable ring system, containing at least one anthracene nucleus, R1 means a radicle of the anthraquinone series, X halogen and n stands for a number from 0 to 4..

The new condensation products are obtained by acting on compounds of the general formula:

wherein R and R1 have the aforesaid significance with alkaline condensation agents under such reaction conditions that no saponification of the carbon amide group occurs. This may be accomplished for instance by heating the initial material together with caustic alkali in indifferent solvents such as for example pyridine or aminoethanol. Thereby ring closure is eifected.

The new dyestuifs thus obtained dye cotton from the vat valuable olive to brown shades of good fastness properties. When aftertreated with halogenating agents, the dyestuffs yield in many cases dyeings which are distinguished by clearer shades and a better fastness to. chlorine.

In order to further illustrate our invention the following examples'are given, the parts being by weight and all temperatures in degrees centigrade.

Example 1 V 47 parts of 1-aminoanthraquinone-6- or '7- carboyl-1-aminoanthraquinone (which may be prepared for instance by reducing the, corresponding nitro compound) are mixed. with 3;. parts of-bzrbromorbenzanthrone,25 parts of sodium acetate and 2 parts of cuprous chloride, and the mixture is boiled for about 12 hoursin nitro-v benzene. The condensation productf-ormedsis separated in the usual manner and dried. It: is soluble in concentrated sulfuric acid with aye l lowish-brown color and dyes cotton from a brownish-violet vat brown shades which do not possess particular fastness properties.

50 parts of this condensation product are finely divided in a solution of 50 parts of caustic potash in about 250 parts Of aminoethanol and the mixture is heated to -110 for about 2 hours. Then the dyestufi formed is precipitated by diluting the mixture with water and blowing through a stream of air, or also by the addition of an acid. The new dyestufi of the formula:

genated dyestufi is obtained which is separated when cool and substantially corresponds to the formula:

O 7 It is soluble in concentrated-sulfuric acid with a green colour and dyes cotton from a bluish-black vat more bluish olive-green shades- The fastness properties of the dyeing-sthus obtained, har-v ticularly the fastness to chlorine, are better. than those of the dyestufi which has not been subjected to such aftertreatment. J

A similar dyestufi is obtained when introducing about 2 atoms bromine into the aforesaid con- 4 densation product. The introduction may beeffected in the usual manner, for instance by treatment with bromine in the presence of an organic solvent.

' Example 2- A mixture of 59 partsof I-aminoanthraquinone 6: '7-) carboyl l--- amino-' -benzoly1amino-anthraquinone, obtainable by reducing the corresponding nitrocompound by means of so- 7 d'mm- -sulflde, and of'31'parts or bzi-bromben'zanthrone is, heated with the addition of an' acid binding-agent and of; a copper'salt as catalyst for 'so'mefhours the presence of boiling 'nitrobenz ene. The condensation "product is soluble in concentrated sulfuric acid with a brown color and l g-g l A Example 3 g 'In an analogous manner as described in Example 2 59 parts of l-amino-anthraquinone-G- dyes cotton'brown shades from a vipletish black 7 Vat. V

'50 -parts thereof are mixed with a-solution of Gil-parts of caustic potash" in about 300 parts of aminoethanol and the mixture is heated while stirring for about 3' hours at about 110; The formed dyes tufl" is isolated after having diluted the reaction mass' with water. It'dissol-ves'in concentrated sulfuric acid with a green color and dyescotton froma bluish black vat very strong yellowishoiivegreenshades.

By treatmentwith, 2 m3 molecular proportions of sulfuryl' chloride in the presence of an organic solvent a halogenated =dyestuff is formed which corresponds substantially to the formula:

ftzeuesnottonifr ma blackish vat valuable olivereen shades. By treatment withA to 6. olecu- 1 larnroportions of; bromi e he n logous bro minated-d-yestufr is obtained of similar properties.

,(-'7-) -carboyl'-1'-amino-4' benzoylaminoanthraquinone, obtainable by reducting the correspond- 12 nitrocompound by dissolving it in the vat, are

condensed. with 31 parts of bzi-bromo-benzanthrone; The condensation product dissolves in concentrated sulfuric acid with a reddish brown color and dyes cotton from a violetish black vat brownishred'shades. It is treated with a caustic potash solution in aminoethanol as described in The formed dyestufi of the foregoing examples. the formula:

0 in AC) YNH-OQQ and cuprous chloride as catalyst. The condensation product dissolves, in concentrated sulfuric ac d with a brownish color and dyes cotton brownish shades from a violetish brown vat.

A mixture of 20 parts of the finely dividedcondensation product and of a solution of 20 parts of caustic potash in about 150 parts of aminoethanol dissolves in concentrated sulfuric acid with a is heated for about 2-3 hours at about 110", The green color and dyes cotton from a blackish vat formed dyestufi is isolated by adding water and valuable khaki shades.

blowing inair. It corresponds with the formula: The chlorinated dyestuifobtained by treat? 0 NH NH 0" l :1 Q: n o=o o i H r It dissolves in concentrated sulfuric acid with a 20 ment with 2 to 3 molecular proportions, of sulgreen color and dyes cotton fast olive shades from furylchloride in the presence of an organic solabrownish black vat. vent dyes somewhat more greenish shades of an increased fastness.

Exam? 5 When subjecting to the action of a mixture of 60 parts of q -fi- 25 caustic potash and aminoethanol the condensar y y n n q e tion product of one molecular proportion of 6-bz1 are condensed as described above with 20 parts dibromobenzanthrgne and 2 1 1 properof 6-bz1-dibromo-benzanthrone. The condentions of l-aminoanthraquinone-fi-(-7-)carboylsation product dissolves in concentrated sulfuric 1' amino 4 benzoylaminoanthraquinone ,the

acid with a brown color and dyes cotton brown- 30 formed dyestufi dyes cotton reddish brown shades ish shades from a dark brown vat. When treatfrom a brownish black vat. It corresponds to the ed with a mixture of caustic potash and aminoformula:

ethanol in the manner as described in Example the formed dyestufi of the formula:

corresponds to the formula:

A mixture of 4'7 parts of maeaeinrequmen'e;

6- (-7-) carboylel -,aminoanthraquinone, ,40 parts of '6-bz1-dibromobenzanthrone, 24parts of sodium acetate, 2 parts of cuprous acetate and about 1000 7 parts of nitrobenzene i heated at about 200 for jprous chloride is added Then the mixture is heated for about 12 hours at about 220".

The formed anthrimide-like condensation product is then subjected to the action of a mixture of caustic potash and aminoethanol as described in the Weiclaim: i f I 1 I. Vat dyestufis' of the'lanthraquinonefseriesiof thegenera-lformulaz wherein R stands for a member of thegroup'consisting of hydrogen and the radicle of an amine foregoing examples. The dyestufi thu obtained 15 of a vattable ring system, containing at leastponc dissolves in concentrated sulfuric acid with a green color and dyes the vegetable fibers from a brownish black vat very fast olive shades. It

As third componentlfor' the aforesaid series of" condensation reactions there may be used instead of l-aminoanthraquinone other amines oiivattab1e ring systems; such as .l-amino-i-methoxy-an-r thraquinone, amino compounds of the anthrapyrimidine, dibenzanthrone and anthranthronel series. When using a diamino compound, such as 1.5-diamino-anthraquinone, of course a dyestufi is obtained containin twice the condensed radicle as represented by the above formula.

anthracene nucleus, R1 means a, radicle of the anthraquinone series, the carbonyl amide radical is attached to one of the positions 6 and 7, X halogen and TL stands for a number from 0 to 4, which dyestufis dye the vegetable fibers from the vat "valuable olive to brown shades of good fastness properties/V 2. The vat dyestufi of the formula:

wherein the carbonyl amide radical is attached to one of the positions '6 and 7 which dyestufi is soluble in concentrated sulfuric acid with a green color and dyes cotton from a bluish black vat blu- "ish olive-green shades of good fastness particularly to chlorine."

3. The vat dyestu fi ofthe formula:

wherein the carbonyl amide radical is attached wherein the carbonyl amide radical is attached to one of the positions 6 and 7 which dyestuff is to one of the positions 6 and 7 which dyestufl soluble in concentrated sulfuric acid with a green dissolves in concentrated sulfuric acid with a color and dyes cotton from a blackish vat olive green color and dyes cotton from a'brownish black green shades of a good fastness. vat fast olive shades. e

4. The vat dyestufi of the formula: 1

' 0 NH- NH 0 /II\ I I ll 0 NH Y o= ll 0 WERNER ZERWECK. ERNST HONOLD. 

